Organic Geochemistry最新文献_第4页

Occurrence and significance of des-A-triterpenoids in the Shahejie formation, Laizhouwan Sag, Bohai Bay Basin: Insights into paleoenvironmental conditions and organic matter origin 渤海湾盆地莱州湾凹陷沙河街组des- a -三萜的赋存状态及意义：古环境条件与有机质成因

IF 2.5 3区地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS

Organic Geochemistry

Pub Date : 2025-12-01 Epub Date: 2025-11-25 DOI: 10.1016/j.orggeochem.2025.105093

Ning Wang , Yaohui Xu , Guo Chen , Sijun Wang

An abundant and diverse suite of des-A-triterpenoids was identified in samples from the Shahejie Formation of the Laizhouwan Sag, Bohai Bay Basin. This suite includes unsaturated des-A-triterpenes, saturated des-A-triterpanes, des-A-nor-series compounds, and mono-, di-, and tri-aromatic des-A-triterpenoids. Compound-specific carbon isotope data of individual hydrocarbons, combined with their co-occurrence and correlation with oleanane, indicate a terrestrial higher plant origin for des-A-oleanane in the studied samples. Significant differences are observed in the geochemical characteristics and the types/abundance of des-A-triterpenoids among the three sections (A, B, and C) of the third member of the Shahejie Formation (E₂s³) from top to bottom. These variations reflect discernible changes in the depositional setting and biological source inputs. Integrating sedimentological evidence with the distribution patterns of des-A-triterpenoids, we propose that the sediments in Section A were deposited in a pro-delta environment. Extensive swamp/marsh environments were likely developed between the lacustrine basin of the Laizhouwan Sag and the adjacent paleo-uplifts (e.g., the Laibei low uplift and the Weibei uplift). High-energy fluvial systems transported substantial amounts of terrigenous higher plant debris from these swamps, providing abundant organic precursors for the formation of des-A-triterpenoids. Furthermore, rapid burial and low thermal maturity (immature stage) are identified as critical factors for the exceptional preservation of these compounds, particularly the less stable des-A-triterpenes, in Section A. In contrast, samples from Sections B and C exhibit a marked decrease in both the diversity and abundance of des-A-triterpenoids. The biomarker composition suggests a reduced contribution from terrestrial higher plants and a corresponding increase in aquatic-derived organic matter. This shift indicates that the fan-delta depositional system prevalent during the deposition of Section A was no longer active. Instead, the environment likely transitioned to a littoral to shallow lacustrine setting during the deposition of these lower sections.

在渤海湾盆地莱州湾凹陷沙河街组样品中发现了丰富多样的des- a -三萜。该组合包括不饱和的双a -三萜，饱和的双a -三萜，双a -非系列化合物，以及单，二，三芳香的双a -三萜。单个碳氢化合物的碳同位素数据，结合它们与齐墩烷的共现和相关性，表明研究样品中的des- a -齐墩烷来自陆生高等植物。从上至下，沙河街组（E2s3）三段A、B、C段的地球化学特征和des-A-三萜的类型/丰度存在显著差异。这些变化反映了沉积环境和生物源输入的明显变化。综合沉积学证据和des-A-三萜的分布格局，我们认为A剖面沉积于前三角洲环境。莱州湾凹陷湖盆与邻近的古隆起（如莱北低隆起和渭北隆起）之间可能发育广泛的沼泽环境。高能河流系统运送了大量来自这些沼泽的陆源高等植物碎屑，为des- a -三萜的形成提供了丰富的有机前体。此外，快速埋藏和低热成熟度（未成熟阶段）被认为是这些化合物特别保存的关键因素，特别是不太稳定的des- a -三萜，在a部分。相比之下，来自B和C部分的样品显示des- a -三萜的多样性和丰度都显着下降。生物标志物组成表明陆生高等植物的贡献减少，水生有机质的贡献相应增加。这一转变表明，A段沉积时期盛行的扇三角洲沉积体系已不再活跃。相反，在这些较低剖面的沉积过程中，环境可能转变为沿海到浅湖的环境。

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引用次数: 0

Isotopic signatures of organic matter in the Upper Miocene–Pliocene Elbistan coal seam (Turkey): Insights from δ13C and δ15N variability 上中新世—上新世Elbistan煤层有机质同位素特征：来自δ13C和δ15N变率的启示

IF 2.5 3区地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS

Organic Geochemistry

Pub Date : 2025-12-01 Epub Date: 2025-10-27 DOI: 10.1016/j.orggeochem.2025.105086

Hatice Kara , Mehmet Ali Ertürk , Leyla Kalender , Cihan Yalçın , Mehmet Deniz Turan , Emine Cicioğlu Sütçü

This study examines the stable carbon (δ¹³C) and nitrogen (δ¹⁵N) isotope compositions of coal samples from the Upper Miocene–Pliocene (Neogene) Elbistan Basin, Turkey, to constrain the sources of organic matter and the depositional conditions of peat formation. A vertical sequence of samples collected from the Kışlaköy open-pit mine was analysed for total carbon and nitrogen contents, C/N ratios, and δ¹³C–δ¹⁵N values. The δ¹³C values range from −28.09 ‰ to −16.99 ‰, while δ¹⁵N values vary between 1.97 ‰ and 4.99 ‰. The carbon isotope data indicate a predominantly C₃-type plant origin for the organic matter, with minor C₄ contributions inferred from samples exhibiting enriched δ¹³C signatures. Although some δ¹³C enrichment may partly reflect microbial alteration of organic matter, the overall values remain consistent with a dominant C₃ vegetation signal. Elevated δ¹⁵N values suggest fluctuating redox conditions and microbial nitrogen cycling during peat accumulation. In comparison with other Turkish lignite basins and global coal deposits, the Elbistan samples display a broader isotopic range, reflecting a more complex paleoenvironmental evolution. The data suggest that the coal beds formed mainly in freshwater mire settings, where fluctuating water tables, variable redox conditions, and occasional inputs from C₄ plants influenced peat accumulation. These results provide new insights into the paleobotanical and geochemical history of the basin and demonstrate the value of stable isotope analysis for reconstructing depositional environments in coal-bearing successions.

研究了土耳其Elbistan盆地上中新世—上新世（新近系）煤样的稳定碳（δ13C）和氮（δ15N）同位素组成，以限制有机质来源和泥炭形成的沉积条件。对采自Kışlaköy露天矿的垂直序列样品进行了总碳、总氮含量、C/N比值和δ13C -δ15N值分析。δ13C值在−28.09‰~−16.99‰之间，δ15N值在1.97‰~ 4.99‰之间。碳同位素数据显示有机质以c3型植物来源为主，δ13C特征丰富的样品显示少量的C4贡献。虽然部分δ13C富集可能部分反映了有机质的微生物蚀变，但总体值与C3植被信号保持一致。δ15N值的升高表明泥炭积累过程中氧化还原条件和微生物氮循环的波动。与土耳其其他褐煤盆地和全球煤层相比，Elbistan样品显示出更广泛的同位素范围，反映了更复杂的古环境演化。数据表明，煤层主要形成于淡水沼泽环境，其中波动的地下水位、可变的氧化还原条件和偶尔的C4植物输入影响了泥炭的积累。这些结果为盆地的古植物学和地球化学历史提供了新的认识，并证明了稳定同位素分析在重建含煤演替沉积环境中的价值。

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引用次数: 0

Definitive identification of Ordovician-sourced oils in the Tarim Basin: geochemical constraints from biomarkers and sulfur isotopes 塔里木盆地奥陶系烃源油的最终鉴定：来自生物标志物和硫同位素的地球化学约束

IF 2.5 3区地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS

Organic Geochemistry

Pub Date : 2025-12-01 Epub Date: 2025-11-29 DOI: 10.1016/j.orggeochem.2025.105096

Daowei Wang , Chunfang Cai , Haijun Yang , Zicheng Cao , Qinghua Wang , Hao Zhang , Peng Sun , Weiquan Zhao , Wei Wang , Zhengzhong Liang , Haoyu Zhang , Qinghua Zheng

The origin of Paleozoic oils in the cratonic Tarim Basin, China, has long been debated, with previous studies attributing most oils to the Cambrian sources. However, the geochemical characteristics and distribution of the Ordovician-sourced oils remain poorly constrained. This study integrates biomarkers, carbon isotopes, and sulfur isotopes to identify the Ordovician-derived oils in the western part of the Shuntuoguole Low Uplift. Two oils (SHB7 and SHB71X) produced from the Ordovician exhibit distinct geochemical signatures, including the absence of aryl isoprenoids, high concentrations of C₃₀ diahopane, elevated Pr/Ph ratios, and low DBT/P ratios, indicative of a clay-rich, suboxic depositional environment. Critically, these oils display significantly lighter bulk δ³⁴S values (4.0‰ and –1.6‰), which closely match those of the Middle-Upper Ordovician kerogen (–6.7‰ to 5.6‰) and are distinctly lower than the Cambrian-sourced oils (15.8‰ to 23.2‰). Individual n-alkanes δ¹³C compositions further support a different genetic origin compared to the typical Cambrian-derived oils. These findings confirm the existence of a previously unrecognized Ordovician-sourced petroleum system in the basin. The distribution of such oils is likely controlled by migration from the Ordovician source kitchens in the Awati Depression or intra-platform depressions. This study underscores the superiority of sulfur isotopes over conventional biomarkers in resolving complex oil-source correlations in multi-source basins like Tarim.

摘要塔里木克拉通盆地古生代原油的来源一直存在争议，以往的研究认为大部分原油来自寒武纪。然而，对奥陶系烃源岩的地球化学特征和分布仍然知之甚少。综合生物标志物、碳同位素、硫同位素等指标，对顺脱郭勒低隆起西部奥陶系烃源岩进行了识别。奥陶系SHB7和SHB71X两种油具有明显的地球化学特征，包括缺乏芳基类异戊二烯，C30二藿烷浓度高，Pr/Ph值升高，DBT/P值较低，表明其沉积环境富含粘土，属于亚氧环境。重要的是，这些油的δ34S值明显较轻（4.0‰~ -1.6‰），与中-上奥陶统（-6.7‰~ 5.6‰）接近，明显低于寒武系（15.8‰~ 23.2‰）。与典型的寒武纪原油相比，单个正构烷烃δ13C组成进一步支持了不同的成因。这些发现证实了盆地中存在一个以前未被认识的奥陶系油气系统。这些油的分布可能受到奥陶系烃源灶在阿瓦提凹陷或台内凹陷的运移控制。该研究强调了硫同位素在解决塔里木等多源盆地复杂油源相关性方面的优势。

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引用次数: 0

Transformation of lignin and lipid biomarkers through degradation of plant tissues and soil organic carbon in a salt marsh-mangrove ecotone 盐沼-红树林交错带植物组织和土壤有机碳降解过程中木质素和脂质生物标志物的转化

IF 2.5 3区地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS

Organic Geochemistry

Pub Date : 2025-12-01 Epub Date: 2025-10-14 DOI: 10.1016/j.orggeochem.2025.105084

Prakhin Assavapanuvat , Joshua L. Breithaupt , Ding He , Ralph N. Mead , Thomas S. Bianchi

The poleward expansion of mangroves into native salt marshes, because of global warming, has the potential to alter coastal soil organic carbon (SOC) stocks and composition. However, its effects on organic carbon decomposition remain largely unknown. This study compared concentrations and degradation indices of lignin, sterol, triterpenoid, and n-alkane biomarkers between live-and-dead leaf-and-root tissues and SOC down to 45-cm depth across habitats dominated by two mangrove and two salt marsh species in Apalachicola coastal wetlands, Florida, USA. A significant increase in n-alkanes and lignin oxidation products was observed following the senescence of Avicennia germinans mangrove tissues. Dead leaves of all four plant species, especially Spartina alterniflora and Juncus roemerianus salt marshes, became hotspots of fungal colonization as indicated by elevated ergosterol content. Interpretation of biomarker degradation ratios was complicated by their large difference between living root and leaf endmembers. In soil cores from all plant habitats, the predominance of tetracyclic triterpenoid degradation products (tetracylic:pentacylic ratio = 0.6–518) indicated prevalent anaerobic decomposition, agreeing with higher cholestanol/cholesterol and stigmastanol/stigmasterol ratios in SOC (0.53 ± 0.29 and 1.14 ± 0.83), relative to plant tissues (0.16 ± 0.17 and 0.57 ± 0.44, respectively). In contrast, the presence of pentacyclic degradation products in deep mangrove and salt marsh soils suggested localized aerobic degradation, likely due to subsurface oxygen release from plant roots. In conclusion, salt marsh-to-A. germinans mangrove replacement modified degradability of surface litter, yet degradation of deep SOC was more dependent on biogeochemical characteristics of the soils.

由于全球变暖，红树林向极地扩张成为原生盐沼，有可能改变沿海土壤有机碳（SOC）储量和组成。然而，它对有机碳分解的影响在很大程度上仍然未知。本研究比较了美国佛罗里达州Apalachicola沿海湿地2种红树林和2种盐沼物种45 cm深度下叶、根活组织中木质素、甾醇、三萜和正构烷烃生物标志物的浓度和降解指数。在红树组织衰老后，正构烷烃和木质素氧化产物显著增加。麦角甾醇含量的升高表明，4种植物的枯叶都成为真菌定植的热点，尤其是互花米草和秋葵盐沼。生物标志物降解率的解释由于其在活着的根和叶末端成员之间的巨大差异而变得复杂。在所有植物生境的土壤岩心中，四环三萜降解产物（四环：五环比= 0.6-518）的优势表明厌氧分解普遍存在，这与有机碳中胆固醇/胆固醇和豆甾醇/豆甾醇的比值（0.53±0.29和1.14±0.83）相对于植物组织（分别为0.16±0.17和0.57±0.44）较高一致。相比之下，深红树林和盐沼土壤中五环降解产物的存在表明局部有氧降解，可能是由于植物根系释放的地下氧。综上所述，盐沼对a。红树林的更替改变了地表凋落物的可降解性，但深层有机碳的降解更多地取决于土壤的生物地球化学特征。

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引用次数: 0

Exploring clumped isotope fractionation of organic molecules using density functional theory 利用密度泛函理论探索有机分子的团块同位素分馏

IF 2.5 3区地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS

Organic Geochemistry

Pub Date : 2025-12-01 Epub Date: 2025-10-07 DOI: 10.1016/j.orggeochem.2025.105062

Alexis Gilbert , Jakub Surma , Naizhong Zhang , Sebastian Danielache , Qi Liu

The measurement of doubly-substituted (‘clumped’) isotopologues provides important information regarding the source, sink, and potentially the temperature of formation of a given molecule. While currently limited to small molecules such as methane or carbonate, recent technological developments are expected to expand the range of molecules studied, paving the way for clumped isotope measurements in various organic compounds. Theoretical calculations, including those based on density functional theory (DFT), can serve as guidelines for future methodological developments. However, these calculations have so far been reported for a small number of organic molecules and clumping types.

Here, we report DFT calculations for DD, ¹³CD, ¹³C¹³C, ¹³C¹⁵N, and ¹³C¹⁸O clumping in organic molecules. Using 32 model molecules, we calculate a total of 143 Δ values (Δ representing the deviation from the stochastic distribution due to equilibrium isotope effects) at temperatures ranging from 300 K to 1000 K. The overall trend follows: ΔDD > Δ¹³CD > Δ¹³C¹⁸O > Δ¹³C¹³C ≈ Δ¹³C¹⁵N, with values decreasing as temperature increases. Through multiple correlation analysis, we demonstrate that the reduced mass of the atoms, bond multiplicity, and hybridization collectively explain 80 % of the differences observed between bond types. Given current analytical uncertainties, the potential for a geothermometer is primarily limited to DD and ¹³CD clumping, while ¹³C¹³C, ¹³C¹⁵N, and ¹³C¹⁸O clumping could be applicable at low temperatures (typically 100 K) or with instrumental precision one order of magnitude higher.

The calculations presented here provide a framework to assess the instrumental precision required for utilizing clumped isotopes in organic molecules as geothermometers. Future improvements in analytical techniques and computational methodologies could further refine these predictions and broaden the applicability of clumped isotope thermometry in organic geochemistry.

双取代（“团块”）同位素的测量提供了关于给定分子的源、汇和潜在形成温度的重要信息。虽然目前仅限于甲烷或碳酸盐等小分子，但最近的技术发展有望扩大研究分子的范围，为各种有机化合物的团块同位素测量铺平道路。理论计算，包括基于密度泛函理论（DFT）的理论计算，可以作为未来方法论发展的指导方针。然而，到目前为止，这些计算只报道了少数有机分子和结块类型。本文报道了有机分子中DD、13CD、13C13C、13C15N和13C18O聚块的DFT计算。使用32个模型分子，我们在300 K到1000 K的温度范围内计算了143个Δ值（Δ表示由于平衡同位素效应而与随机分布的偏差）。总体趋势如下：ΔDD >； Δ13CD >； Δ13C18O >； Δ13C13C≈Δ13C15N，随温度升高而减小。通过多重相关分析，我们证明原子质量的减少、键的多样性和杂化共同解释了80%的键类型之间的差异。鉴于目前的分析不确定性，地温计的潜力主要局限于DD和13CD的聚类，而13C13C、13C15N和13C18O的聚类可能适用于低温（通常为100 K）或仪器精度高一个数量级。这里提出的计算提供了一个框架，以评估利用有机分子中的团块同位素作为地温计所需的仪器精度。分析技术和计算方法的未来改进可以进一步完善这些预测，并扩大团块同位素测温在有机地球化学中的适用性。

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引用次数: 0

Insights into the complex nature of dissolved organic matter from plant residues using multiple spectroscopic techniques 利用多光谱技术深入了解植物残留物中溶解有机物的复杂性质

IF 2.5 3区地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS

Organic Geochemistry

Pub Date : 2025-12-01 Epub Date: 2025-11-25 DOI: 10.1016/j.orggeochem.2025.105095

Zongtang Yang , Biswaranjan Mohanty , Feike A. Dijkstra , Georg Guggenberger , Balwant Singh

Dissolved organic matter (DOM) is the most active and labile organic fraction in soils, participating in numerous biogeochemical processes. Comprehensive understanding of DOM composition at the molecular level remains a challenge due to limited or contrasting analytical data based on a single technique or limited analysis, which may be addressed using multiple complementary techniques. In this study, we utilized five prevalent and novel spectroscopic and spectrometric techniques, i.e., XPS, FTIR, NEXAFS, NMR, and FT-ICR-MS, coupled with multivariate analysis to decipher the complexity of DOM. We extracted DOM from four decomposed plant residues − pine, eucalyptus, pasture, and wheat. The organic carbon concentration in the DOM samples followed the order: pine > eucalyptus > wheat > pasture. Eucalyptus and pasture DOM exhibited similarities in aromatic compounds but differed in saturation and O-containing groups. Pine DOM was enriched in aromatic and carboxylic compounds, whereas wheat DOM contained more lipid and aliphatic compounds. The differences in the abundance of functional groups and compound families were attributed to the influence of both the original plant residues and microbial degradation. Chemical convergence of the four DOM samples, reflected by their broadly similar spectral composition was possibly due to similar biodegradation processes but in different stages. Multivariate analysis of multiple spectroscopic data comprehensively captured the DOM composition.

溶解有机质（DOM）是土壤中最活跃、最不稳定的有机组分，参与了许多生物地球化学过程。由于基于单一技术或有限分析的分析数据有限或相互对照，因此在分子水平上对DOM组成的全面理解仍然是一个挑战，这可能需要使用多种互补技术来解决。本研究利用XPS、FTIR、NEXAFS、NMR和FT-ICR-MS这五种流行的新型光谱和光谱技术，结合多变量分析来解读DOM的复杂性。我们从松树、桉树、牧草和小麦四种腐烂的植物残体中提取DOM。DOM样品中的有机碳浓度顺序为：松木>；桉树>；小麦>；牧草。桉树DOM和牧草DOM芳香化合物具有相似性，但在饱和度和含o基团上存在差异。松木DOM富含芳香和羧基化合物，而小麦DOM则含有更多的脂质和脂肪族化合物。官能团和化合物族丰度的差异归因于原始植物残留物和微生物降解的影响。四种DOM样品的化学收敛（光谱组成大致相似）可能是由于相似的生物降解过程，但处于不同的阶段。对多光谱数据进行多元分析，全面捕获DOM组成。

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引用次数: 0

Compositional convergence of dissolved organic matter from root litter to rhizosphere soil in a semiarid grassland of North China 华北半干旱草地凋落根向根际土壤溶解有机质的组成收敛性

IF 2.5 3区地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS

Organic Geochemistry

Pub Date : 2025-12-01 Epub Date: 2025-09-01 DOI: 10.1016/j.orggeochem.2025.105061

Xiaohan Mo , Zongxiao Zhang , Mengke Wang , Qiang Zhang , Guodong Sun , Weifeng Hu , Guoping Chen , Deliang Kong , Chengcheng Dong , Hui Zeng , Junjian Wang

The transformation of litter-derived dissolved organic matter (DOM) in soils is important for carbon cycling in terrestrial ecosystems. However, the linkage between root litter- and rhizosphere soil-derived DOM remains unclear. In this study, using ultrahigh-resolution mass spectrometry and metagenomics, we evaluated the DOM in paired roots and rhizosphere soils for herbaceous plants in a semiarid grassland and their biogeochemical processes. Analyses revealed a decoupling between root- and rhizosphere soil-derived DOM despite being directly attached, with a considerable loss of root-derived aliphatics and proteins, and production of highly unsaturated, aromatic, and carboxyl-rich compounds. From roots to rhizosphere soils, DOM shifted toward a more uniform molecular composition, which was likely the result of a more “specialized” utilization of root-derived DOM and a more “generalized” utilization of rhizosphere soil-derived DOM by the rhizosphere microbial community. Overall, DOM transformation at the root-soil interface occurred along two principal dimensions: 1) the dimension of “root-to-soil variation” with “lability” and “aromaticity” as two end members, and 2) the dimension of “interspecies variation” dominated by bulk and optical DOM components. These findings suggest that root- and rhizosphere soil-derived DOM constitute two distinct carbon sources for rhizosphere microbial communities and provide a framework for future investigations into DOM dynamics and ecosystem functioning at the plant-soil interface.

土壤中凋落物源溶解有机质（DOM）的转化对陆地生态系统的碳循环具有重要意义。然而，根凋落物和根际土壤DOM之间的联系尚不清楚。本研究利用超高分辨率质谱技术和宏基因组学技术，研究了半干旱草地草本植物根际和根际配对土壤中的DOM及其生物地球化学过程。分析表明，尽管根际土壤来源的DOM直接附着，但根际土壤来源的DOM之间存在解耦，根际土壤来源的脂肪和蛋白质大量流失，并产生高度不饱和、芳香和富含羧基的化合物。从根到根际土壤，DOM的分子组成趋于统一，这可能是根际微生物群落对根源DOM的利用更加“专门化”，对根际土壤源DOM的利用更加“普遍化”的结果。总体而言，根-土界面DOM的转化主要发生在两个维度上：1)以“不稳定性”和“芳香性”为两端成员的“根-土变异”维度，2)以体积和光学DOM成分为主的“种间变异”维度。这些发现表明，根际和根际土壤来源的DOM构成了根际微生物群落的两种不同的碳源，并为未来研究植物-土壤界面DOM动态和生态系统功能提供了框架。

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引用次数: 0

Obituary for Prof. Dr. Dietrich Welte (1935–2025) 迪特里希·韦尔特教授讣告（1935-2025）

IF 2.5 3区地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS

Organic Geochemistry

Pub Date : 2025-11-01 Epub Date: 2025-07-31 DOI: 10.1016/j.orggeochem.2025.105047

引用次数: 0

Geochemistry articles – May 2025 地球化学文章- 2025年5月

IF 2.5 3区地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS

Organic Geochemistry

Pub Date : 2025-11-01 Epub Date: 2025-07-10 DOI: 10.1016/j.orggeochem.2025.105043

引用次数: 0

Deamination of alicyclic and aromatic amines under geologically relevant hydrothermal conditions 与地质相关的热液条件下脂环胺和芳香胺的脱胺作用

IF 2.5 3区地球科学 Q2 GEOCHEMISTRY & GEOPHYSICS

Organic Geochemistry

Pub Date : 2025-11-01 Epub Date: 2025-08-31 DOI: 10.1016/j.orggeochem.2025.105060

Yiju Liao , Alexandria Aspin , Xuan Fu , Kirtland Robinson , Ziming Yang

Amines are a particular group of organic compounds of interest to deep-sea biology, organic geochemistry, and astrobiology research, in large part due to their involvement in biological metabolism, such as in the form of amino acids and proteins, participation in the subsurface carbon (C) and nitrogen (N) cycles, as well as their relevance to biomolecular precursors on early Earth and potential biosignatures beyond Earth. Although there have been many studies on the deamination of amines under hydrothermal conditions, few have determined the relative deamination rates and degradation mechanisms among different amine structures. In this study, we investigate the reaction kinetics and pathways of a group of aromatic and alicyclic amines, including aniline, benzylamine, cyclohexylamine, and cyclohexylmethylamine, under geologically relevant temperatures (200–275 °C) and pH ranges (5–9) for up to 120 h. Among the studied amines, the amine reactivity generally follows a trend of aniline < cyclohexylamine < cyclohexylmethylamine < benzylamine. Alcohols and secondary amines/imines are observed as the major products of amines, whose formation could follow a nucleophilic substitution (S_N1 or S_N2) mechanism. Hydrothermal experiments at different pH also show that deamination occurs more readily under acidic than alkaline hydrothermal conditions, indicating that the aminium form (R-NH₃⁺) accelerates deamination. These results suggest that the kinetics and pathways of hydrothermal amine transformations are controlled by both the amine structure and solution pH, which have implications for predicting the deamination processes of organic N, release of inorganic N (e.g., ammonia), and N cycling in geologically relevant hydrothermal systems.

胺是深海生物学、有机地球化学和天体生物学研究感兴趣的一类特殊有机化合物，这在很大程度上是因为它们参与生物代谢，例如以氨基酸和蛋白质的形式，参与地下碳(C)和氮(N)循环，以及它们与早期地球上的生物分子前体和地球以外潜在的生物特征的相关性。虽然对水热条件下胺类物质的脱氨作用研究较多，但对不同胺类结构间的相对脱氨速率和降解机理的研究较少。在本研究中，我们研究了苯胺、苄胺、环己胺和环己基甲胺等芳香族和脂环类胺在地质相关温度（200-275℃）和pH（5-9）下长达120 h的反应动力学和反应途径。在所研究的胺中，胺的反应性总体上遵循苯胺、环己胺、环己基甲胺和苄胺的变化趋势。醇和仲胺/亚胺是胺的主要产物，其形成遵循亲核取代（SN1或SN2）机制。不同pH条件下的水热实验也表明，酸性水热条件下脱氨比碱性水热条件下更容易发生，说明氨形态（R-NH3+）加速了脱氨。这些结果表明，水热胺转化的动力学和途径受胺结构和溶液pH的共同控制，这对预测地质相关热液系统中有机氮的脱氨过程、无机氮（如氨）的释放和氮循环具有重要意义。

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引用次数: 0